One-Step Carrier Modulation and Nano-Composition Enhancing Thermoelectric and Mechanical Properties of p-Type SnSe Polycrystals by Introducing Ag9GaSe6 Compound

doi:10.1007/s40195-024-01810-0

Abstract

Abstract:

The group IV-VI semiconductor, SnSe, is abundant on the earth and is a promising thermoelectric (TE) material due to its low thermal conductivity. However, the p-type SnSe polycrystals have low electrical conductivities due to their low carrier concentration, significantly limiting their further applications. This study introduced the argyrodite-type Ag₉GaSe₆ compound into the SnSe matrix to effectively increase the hole carrier concentration, increasing the electrical conductivity. A high electrical conductivity of 50.5 S cm⁻¹ was obtained for the SnSe + 0.5 wt% Ag₉GaSe₆ sample at 323 K. Due to the increased electrical conductivity, the SnSe + 0.5 wt% Ag₉GaSe₆ sample had an average power factor (PF_ave) value of ~ 410 μW m^-1 K^-2 in the 323-823 K temperature range, a nearly four times enhancement compared to the undoped SnSe sample. Additionally, the thermal conductivity slightly increased due to the introduction of the Ag₉GaSe₆ compound. However, the electrical transport properties were significantly enhanced, making up for the improvement in thermal conductivity. Consequently, the SnSe + 0.5 wt% Ag₉GaSe₆ sample obtained a peak thermoelectric figure of merit ZT value of ~1.2 at 823 K and a ZT_ave value of 0.58 in the 323-823 K temperature range. The proposed strategy improved the ZT and ZT_ave values of SnSe-based TE materials at room temperature and provided a systematic strategy for modifying SnSe-based TE materials. Moreover, the thermoelectric properties of SnSe can be effectively improved by introducing the Ag₉GaSe₆ compound for doping, and waste heat power generation can be effectively carried out in the middle temperature region.

Key words: p-Type polycrystalline SnSe, Thermoelectric materials, Nanoscale second phase, Electrical conductivity

Ze Li, Xing Yang, Tian-En Shi, Wang-Qi Bao, Jing Feng, Zhen-Hua Ge. One-Step Carrier Modulation and Nano-Composition Enhancing Thermoelectric and Mechanical Properties of p-Type SnSe Polycrystals by Introducing Ag₉GaSe₆ Compound[J]. Acta Metallurgica Sinica (English Letters), 2025, 38(5): 781-792.

Figures/Tables 9

Fig. 1 a Layered structure of carrier introduction and phonon scattering diagram, b the change of the electrical conductivity and PF value, c comparison with several reported ZT value of p-type polycrystalline SnSe-based materials doped by Ag2Se [33], Ag2S [54], Zn [29], AgInSe2 [55], Sb [56], Pb [57] and other works [22,28,58]

Fig. 2 a XRD patterns of SnSe + x wt% Ag9GaSe6 (x = 0, 0.125, 0.25, and 0.5) bulk samples, b enlarged XRD image of a narrow angle from 30° to 32°, c measured TG-DSC curves indication from room temperature to 1400 K for Ag9GaSe6 but a phase transition around 1028 K

Fig. 3 Different directions of SEM images of the fractured surfaces for SnSe + x wt% Ag9GaSe6 (x = 0, 0.125, 0.25, 0.5, and 1) bulk samples: a SnSe, b x = 0.125, c x = 0.25, d x = 0.5, e x = 1.0; f experiment density and relative density

Fig. 4 EPMA results providing the elemental distribution of the elemental distribution of the SnSe + 0.5 wt% Ag9GaSe6 sample: a back scattered electron (BSE) image, b-e elemental mapping of Sn, Se, Ag, and Ga

Fig. 5 TEM images of SnSe + 0.5 wt% Ag9GaSe6 bulk samples: a typical STEM image, b the corresponding FFT image, c high-resolution STEM image, d partial enlarged drawing of d, e inserted fast Fourier transformation (IFFT) image of d, f stress distribution of the whole region in d by geometric phase analysis (GPA), and the color bar represents -10% to 10% strain; a1-a4 EDS element mapping of the area in a, indicating that precipitates in the bulk composite are Ag9GaSe6

Fig. 6 Temperature dependence of electrical transport properties for the SnSe + x wt% (x = 0, 0.125, 0.25, 0.5, and 1.0) bulk samples: a electrical conductivity (σ), b Seebeck coefficient (S), c power factor (PF), d carrier concentration (ne), dependence of the power factor (PF) at room temperature

Fig. 7 Temperature dependence of thermal transport properties for the SnSe + x wt% Ag9GaSe6 (x = 0, 0.125, 0.25, 0.5, and 1.0) bulk samples: a total thermal conductivity (κt), b electron thermal conductivity (κe), and c lattice thermal conductivity (κl)

Fig. 8 Temperature dependence of the SnSe + x wt% Ag9GaSe6 (x = 0, 0.125, 0.25, 0.5, and 1.0) bulk samples: a PFave and ZTave value of p-type polycrystalline SnSe-based materials doped by Ag9GaSe6, b ZT value of all samples

Fig. 9 Hardness and Young’s modulus of a, b SnSe and c, d SnSe + 0.5 wt% Ag9GaSe6 sample

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One-Step Carrier Modulation and Nano-Composition Enhancing Thermoelectric and Mechanical Properties of p-Type SnSe Polycrystals by Introducing Ag₉GaSe₆ Compound

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